CN105561758A - High efficiency wet method for removal of hydrogen sulfide from iron-based ionic liquid - Google Patents
High efficiency wet method for removal of hydrogen sulfide from iron-based ionic liquid Download PDFInfo
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- CN105561758A CN105561758A CN201410539606.2A CN201410539606A CN105561758A CN 105561758 A CN105561758 A CN 105561758A CN 201410539606 A CN201410539606 A CN 201410539606A CN 105561758 A CN105561758 A CN 105561758A
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- ionic liquid
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Abstract
Belonging to the technical field of gas purification, the invention relates to a high efficiency wet method for removal of hydrogen sulfide from iron-based ionic liquid. The desulfurization solution mainly contains iron-based ionic liquid and heteropoly acid ionic liquid, and is immiscible with water. The desulfurization method includes: using the iron-based ionic liquid to absorb and oxidize H2S into elemental sulfur, under the catalysis of the heteropoly acid ionic liquid, employing air to regenerate iron-based ionic liquid, and then subjecting the regenerated iron-based ionic liquid and heteropoly acid ionic liquid to cyclic removal of H2S. Because of the catalytic action of heteropoly acid ionic liquid, the low-temperature oxidation desulfurization rate of the iron-based ionic liquid is greatly improved. According to the invention, the desulfurization solution oxidizes hydrogen sulfide into elemental sulfur, is easy to regenerate, can be recycled, and the desulfurization method has the advantages of simple preparation process, high absorption efficiency, no side reaction, easy recovery of sulfur and the like.
Description
Technical field
The invention belongs to gas purification technique field, relate to a kind of method that efficient wet iron-based ionic liquid removes hydrogen sulfide.
Background technology
In the industrial gasses such as petrochemical industry, natural gas, oil field development, coke-stove gas and semiwater gas, hydrogen sulfide is a kind of very harmful impurity.Its existence not only can cause equipment and corrosion of piping, and can bring quite serious harm to environment, belongs to the pollutant that must eliminate or control.
The hydrogen sulfide of different content can adopt different technical process, and when in acid gas, sulphur concentration is higher, Application comparison generally hydramine absorbs-Claus method desulfurization sulphur technique.And when concentration of hydrogen sulfide is lower or concentration of hydrogen sulfide is higher but the occasion that gas flow is little, what extensively adopt is wet oxidation reducing process desulfurization sulphur technique.The common feature of traditional wet oxidation reducing process desulfurization sulphur technique carries out all in aqueous, especially when it in the basic conditions, there is chelating agent expensive, easily degrade, side reaction aggravation and the problem such as product sulphur is second-rate during sulfur capacity height.
Ionic liquid, be also called ionic liquid at room temperature or room temperature fused salt, the molten salt system be in a liquid state under room temperature or nearly room temperature be made up of specific organic cation and organic or inorganic anion, there is good heat endurance and chemical stability, vapour pressure is extremely low, the advantage such as not volatile, toxicity is very low, structure can design is the novel green medium of a class.
Iron-based ionic liquid [bmim] FeCl
4be a kind of Lewis acid catalyst, the iron ion in iron-based ionic liquid can play oxidation and remove H
2s, the feature of iron-based ionic liquid collection oxidisability, hydrophobicity and good stability, has desulfurization under acid condition, doctor solution without running off and not producing the advantage of secondary salt.
Summary of the invention
The object of the invention is to, provide a kind of heteropoly acid ionic liquid that adds to make iron-based ionic liquid remove H in acid condition
2s is doctor solution and sulfur method more favorably.
Efficient wet iron-based ionic liquid of the present invention removes the method for hydrogen sulfide, it is characterized in that: utilize the doctor solution containing iron-based ionic liquid and heteropoly acid ionic liquid by H
2s is oxidized to elemental sulfur; Course of reaction utilizes iron-based ionic liquid to absorb and is oxidized H
2s becomes sulphur simple substance, under the catalytic action of heteropoly acid ionic liquid, adopts oxygen-containing gas to be regenerated by iron-based ionic liquid; After separated product sulphur simple substance and water, doctor solution circulation is re-used.
Selected iron-based ionic liquid is by iron chloride complex anion and alkyl imidazole cation composition.Iron-based ionic liquid is by prepare after ferric chloride hexahydrate or anhydrous ferric chloride and the abundant mix and blend of chlorination alkyl imidazole.Chlorination alkyl imidazole refers to the imidazole derivative that chlorination is alkyl-modified, imidazoles is including, but not limited to N-methylimidazole, also can be the derivative such as N-ethyl imidazol(e) and N-butyl imidazole, chlorination alkyl is including, but not limited to chloro-butane, also can be chloro-hexane, chloro octane, the alkyl chloride radical derivatives such as chlorinated dodecane.
The effect of heteropoly acid ionic liquid mainly promotes the oxidation of iron-based ionic liquid, and heteropoly acid ionic liquid itself also has redox property.Source of anions, in different heteropolyacid anions, is phosphotungstic anion, silico-tungstic acid anion, phosphomolybdic acid anion.Cation chosen alkyl imidazole cationoid.
Described doctor solution is directly by H
2s is oxidized to sulphur simple substance, does not wherein need the pH regulating doctor solution.
The hydrophobicity of doctor solution refers to mixed ionic liquid and the phase-splitting of water nature, and form liquid-liquid diphase system, water does not dissolve in mixed ionic liquid.
In described doctor solution, the volume ratio of heteropoly acid ionic liquid and iron-based ionic liquid is 1/1 ~ 1/10.
Described desulfurizing agent liquid is applicable to removing of hydrogen sulfide in natural gas, biogas or associated gas, H in process gas
2the concentration range of S is 0.1 ~ 30%(volume fraction).
At ambient pressure, the temperature controlling desulfurization regeneration oxidation step is 20 ~ 100 DEG C to described method.
The oxygen-containing gas used in described desulfurization regeneration oxidizing process, comprises air, oxygen.
Doctor solution containing iron-based ionic liquid and heteropoly acid ionic liquid removes H
2s has following advantage:
1, the Lewis acid performance characteristics of iron-based ionic liquid and heteropoly acid ionic liquid, without the need to adjusting pH.
2, do not have side reaction to generate in solution, in acid condition, the reaction producing carbonate and thiosulfate is also impossible.
3, utilize the hydrophobic property of ionic liquid, the water generated in regenerative process is separated with ionic liquid automatically, avoids ionic liquid to be run off by diluting.
4, under the catalytic action of heteropoly acid ionic liquid, the low-temperature oxidation desulfurization degree of iron-based ionic liquid is greatly improved.
This doctor solution and sulfur method are applicable to removing of hydrogen sulfide in natural gas, biogas or associated gas, H in process gas
2the concentration range of S is 0.1 ~ 30%(volume fraction).
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment 1 adopts containing [bmim] FeCl
4[bmim]
3pMo
12o
40solution removal H
2s
[bmim]
3pMo
12o
40[bmim] FeCl
41/4, preparation 50mL desulfurization ionic liquid by volume.Mixed gas composition H
2s is 10%(V), N
2for 90%(V).Pass in solution with 30ml/h flow, after 5h, the conversion ratio of sulphur is 98%.Then will pass into air regenesis 1h by solution before, heating-up temperature is 40 DEG C.When under above-mentioned the same terms, again pass into mist, the conversion ratio of sulphur is 98%.Circulation like this 4 times, the oxidation catalytic property of solution does not reduce.
Embodiment 2. adopts containing [bmim] FeCl
4[bmim]
3pW
12o
40solution removal H
2s
[bmim]
3pW
12o
40[bmim] FeCl
41/4, preparation 50mL desulfurization ionic liquid by volume.Mixed gas composition H
2s is 10%(V), N
2for 90%(V).Pass in solution with 30mL/h flow.After 5h, the conversion ratio of sulphur is 99%.Then will pass into air regenesis 1h by solution before, heating-up temperature is 40 DEG C.When under above-mentioned the same terms, again pass into mist, the conversion ratio of sulphur is 98%.Circulation like this 4 times, the oxidation catalytic property of solution does not reduce.
Comparative example 1 adopts containing [bmim] FeCl
4but do not add the solution removal H of heteropoly acid ionic liquid
2s
Preparation [bmim] FeCl
4ionic liquid 50mL.Mixed gas composition H
2s is 10%(V), N
2for 90%(V).Pass in solution with 30mL/h flow.After 5h, the conversion ratio of sulphur is 95%.Then will pass into air regenesis 1h by solution before, heating-up temperature is 40 DEG C.When under above-mentioned the same terms, again pass into mist, the conversion ratio of sulphur is 93%.Circulation like this 4 times, because each recovery time is inadequate, causes the oxidation catalysis of solution to be reduced to 90%.
Comparative example 2 adopts containing heteropoly acid ionic liquid but does not add [bmim] FeCl
4solution removal H
2s
Preparation [bmim]
3pMo
12o
40ionic liquid 50mL.Mixed gas composition H
2s is 10%(V), N
2for 90%(V).Pass in solution with 30mL/h flow.After 5h, the conversion ratio of sulphur is 94%.Then will pass into air regenesis 1h by solution before, heating-up temperature is 40 DEG C.When under above-mentioned the same terms, again pass into mist, solution does not reoxidize H
2s, conversion ratio is 0.
Claims (9)
1. efficient wet iron-based ionic liquid removes a method for hydrogen sulfide, it is characterized in that: utilize the doctor solution containing iron-based ionic liquid and heteropoly acid ionic liquid by H
2s is oxidized to elemental sulfur; Course of reaction utilizes iron-based ionic liquid to absorb and is oxidized H
2s becomes sulphur simple substance, under the catalytic action of heteropoly acid ionic liquid, adopts oxygen-containing gas to be regenerated by iron-based ionic liquid; After separated product sulphur simple substance and water, doctor solution circulation is re-used.
2. as claim
1described method, is characterized in that: selected iron-based ionic liquid is by iron chloride complex anion and alkyl imidazole cation composition.
3. as claim
1described method, it is characterized in that: selected heteropoly acid ionic liquid is tool redox property, source of anions, in different heteropolyacid anions, is selected from phosphotungstic anion, silico-tungstic acid anion, phosphomolybdic acid anion, cation chosen alkyl imidazole cationoid.
4. as claim
1described method, is characterized in that: described doctor solution is directly by H
2s is oxidized to sulphur simple substance, does not wherein need the pH regulating doctor solution.
5. as claim
1described method, is characterized in that: the hydrophobicity of doctor solution refers to mixed ionic liquid and the phase-splitting of water nature, and form liquid-liquid diphase system, water does not dissolve in mixed ionic liquid.
6. as claim
1described method, is characterized in that: in doctor solution, the volume ratio of heteropoly acid ionic liquid and iron-based ionic liquid is 1/1 ~ 1/10.
7. as claim
1described method, is characterized in that: this desulfurizing agent liquid is applicable to removing of hydrogen sulfide in natural gas, biogas or associated gas, H in process gas
2the concentration range of S is 0.1 ~ 30%(volume fraction).
8. as claim
1described method, is characterized in that: at ambient pressure, and the temperature controlling desulfurization regeneration oxidation step is 20 ~ 100 DEG C.
9. as claim
1described method, is characterized in that: the oxygen-containing gas used in desulfurization regeneration oxidizing process, comprises air, oxygen.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265722A (en) * | 2017-08-08 | 2017-10-20 | 哈尔滨工业大学 | A kind of method that utilization polyacid ionic liquid realizes Containing Sulfur sodium waste water desulfurization |
| CN107519743A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | A kind of method that iron-based ionic liquid removes hydrogen sulfide and mercaptan simultaneously |
| CN107789960A (en) * | 2016-09-02 | 2018-03-13 | 上海新禹固废处理有限公司 | Iron chloride removes hydrogen sulfide technology |
| CN109381978A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Efficient absorption liquid for indirect electrolytic hydrogen sulfide |
| CN111346490A (en) * | 2020-03-18 | 2020-06-30 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519743A (en) * | 2016-06-20 | 2017-12-29 | 中国石油化工股份有限公司 | A kind of method that iron-based ionic liquid removes hydrogen sulfide and mercaptan simultaneously |
| CN107789960A (en) * | 2016-09-02 | 2018-03-13 | 上海新禹固废处理有限公司 | Iron chloride removes hydrogen sulfide technology |
| CN109381978A (en) * | 2017-08-02 | 2019-02-26 | 中国石油化工股份有限公司 | Efficient absorption liquid for indirect electrolytic hydrogen sulfide |
| CN107265722A (en) * | 2017-08-08 | 2017-10-20 | 哈尔滨工业大学 | A kind of method that utilization polyacid ionic liquid realizes Containing Sulfur sodium waste water desulfurization |
| CN111346490A (en) * | 2020-03-18 | 2020-06-30 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
| CN111346490B (en) * | 2020-03-18 | 2022-02-08 | 山东大学深圳研究院 | Polyacid-based green desulfurization system, desulfurization-electrochemical regeneration synergistic cyclic desulfurization hydrogen byproduct method, system and application |
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